Conjoint polymerization products



-Patented Dec. 4, '1945 'UNlTED STATES: PATENT OFFICE CONJOINT POLYMERIZATION PRODUCTS Eugene W. Mofi'ett, Milwaukee, Wis., and Roy E. Smith,New York, N. Y., assignors to Pittsburgh PlateGlass Company, acorporation of Pennsylvania No Drawing. Original application April 5,1940,

Serial No. 327,996. Divided and this application May 5, 1943, Serial No.485,746

3 Claims.

resulting from such processes frequently differ.

widely in properties from the resins obtained by the simplepolymerization of either monomer alone or of mechanical mixtures of thetwo simple Polymers.

Perhaps the most widely exploited of the copolymers are those of vinylacetate and vinyl chloride known commercially as Vinylite resins. Bothmonomers had been previously polymerized alone to yield resins, each ofwhich was useful for certain specific uses. The copolymers were entirelydifferent from either of the simple resins and were capable of muchwider and more diversified use.

It will be observed that these copolymers are derived from monomers,each of which is readily capable of polymerization alone to a good yieldof a well characterized resin. The new copolymers described in thisdisclosure are derived from one readily polymerizable material and asecond substance most diiiicultly polymerizable. The sim: ple allylesters polymerize with great difiiculty and in very poor yields toresins of low molecular weight and no known utility.

It would normally be anticipated under such circumstances that the'readily polymerizable compound would be converted into resin leavingthe highly inactive allyl esters behind. Such was not found to be thecase, however. The vinyl and allyl esters copolymerized readily undernormal polymerizing conditions using peroxide catalysts to good yieldsof well characterized and useful resins. The process and products aremore fully described herein below.

In the present invention; the allyl esters used correspond to one of thegeneral formulae wherein R is hydrogen or a lower alkyl radical,

R. is hydrogen or a saturated alkyl or aryl radical 55 lacquer base.

- ing material.

and X is chlorine. The vinyl ester used corresponds to one of thegeneral formulae wherein R is hydrogen or a lower saturated alkylradical and X is chlorine, The allyl ester is mixed with the vinyl esterin ratios from about 1 to 50 parts by weight of the former to 50 to 99parts by weight of the latter. The polymerization reaction becomesslower with increasing concentrations of the allyl esters and it isimpractical to use more than an equal weight of the latter Thepolymerizations are carried out in the presence or absence of a diluentand at temperatures suitably in a range between 15 and C. The exactconditions for any given polymerization are selected on the basis of thecharacter of the monomers chosen and the properties desired in theproduct. In general, it is advisable to use a diluent because thereaction is exothermic and may be more readily controlled in thepresence of a diluent. The reactions are carrled out in any suitablevessel taking into account, of course, the character of the monomermaterials. Thus, DOlymerizations in which vinyl acetate is a reactantmay be carried out under reflux in glass at ordinary pressures. Whenvinyl chloride is a reactant a pressure vessel is required. Lead orglass lined steel equipment has been found very satisfactory for thepurpose.

The polymerizations may be catalyzed in the usual manner using light oran organic peroxide such as an benzoyl peroxide and the like.

The new resins vary widely in properties dependin on the character ofthe monomers employed and the conditions of polymerization. They arethermoplastic and, in general, are well characterized solids at roomtemperatures. They are usually soluble in properly selected organicsolvents from solutions in which they may be isolated by precipitationwith a non-solvent or by steam distillation.

The resins are capable of a wide variety of applications. They areunusually stable to the effects of light and heat, a property which isparticularly advantageous in application as a finish- Thus, solutions ofthe allyl acetate-vinyl chloride resin may be coated on iron ortin-plate and the resultin films baked hour at 325-350 F. withoutvisible decomposition. These solutions are likewise characterized by lowviscosity, another advantage when usedasa These properties are alsoadvantageous in other applications of the resin. Molded'into transparentdiscs and the like. they are characterised by unusual stability tolight. Moldings may be made from the resins with or withoutplasticizers, pigments. or dyestuffs, fillers and the like. The resinsmay also be extended M films, filaments and the like and adapted to theuses thereof. The softer of the resins may be used as adhesivesparticularly in applications where color retention and permanentthermoplasticity are required.

Vinyl compounds suitable for use in practicing the invention includingthe vinyl halides, such as vinyl chloride and bromide, the vinyl esters,such as vinyl acetate, vinyl propionate, vinyl butyrate, vinylchloroacetate, vinyl tricholoracetate and any of the otherreadily-polymerizable vinyl compounds. The allyl compounds to.beconiointly polymerized with any of the vinyl compounds include the allyland methallyl halides, such as allyl and methallyl chloride or bromide,allyl alcoho. allyl esters, such as allyl acetate. ally proplonate,allyl butyrate, allyl caproate, allyl linoleate, allyl chloroacetate,allyl trichloroacetate. It will be apparent that mixtures of vinylhalides and vinyl esters may be coniointly polymerized with'an allylcompound. For example, a mixture consisting of 10 to 90% of vinylchloride and the remainder being a vinyl ester, such as vinyl acetate orvinyl butyrate may be coniointly polymerized with allyl chloride, allylalcohol, allyl acetate, or allyl butyrate. The ratio of the allylcompound may be, for example, 10 to 50% of the mixture of vinyl compoundand allyl compound. Mixtures ofallyl compounds, such as allyl alcohol orallyl chloride with allyl acetate or butyrate are contemplated. Thesemixtures of allyl compounds may be incorporated with any one of thevinyl compounds or with the mixtures of vinyl compounds above mentioned.

Solutions of resins in clear state or admixed with pigments such astitanium dioxide in amounts of or or more may be used for coating woodand metal, or for coating fabrics of cotton, rayon, silk, nylon, linenand the like.

The resins herein disclosed in addition to being useful with solvents ascoating compositions are also useful as bonding agents or cements forwood, leather and fiber. Solutions and liquid resins in an amount of 30%or more may be admixed with wood flour or other filler and dried to formpowders which are useful for molding under heat and pressure. Thesolutions and liquid resins may also be spun to form fine fiberssuitable for use in the fabrication of textiles. The use of sheets ofthe clear resins as interlayers in safety glass is contemplated.Similarly, the use of solutions of the resins or of the liquid resins ascements for application to other plastic material, such as celluloseacetate to provide a bond in'safety glass is also contemplated. when theresins are employed as interlayers or as bonds for interlayers forsafety glass, the sheet material is laminated between two or more sheetsof glass by application of heat and pressure, in accordance withconventional methods.

Tin cans and other containers for beer and other food products can becoated with the solutions of the resins and baked to provide surfacefilms, which will resist the action of the contents. Also, paper,Cellophane and other wrapping materials for cigarettes, cheese and othercomestlble products may be coated with the resins. The addition ofmoistureproofing agents. such as paraiiin or other wax, either to theresin solutions, or as discrete films to the surface of the resin films,is contemplated.

The addition of plasticizers, such as diethyl phthalate to the resins iscontemplated Similarly the modification of the resins by the addition ofother resins. such as vinyl resin, in amounts of 5% or more and dryingoils, is within the purview of the invention.

The following examples serve to illustrate the practice of the inventionbut are not to be construed as limiting the scope thereof:

Example 1 A solution consisting of 50 parts by weight of allyl acetate,88 parts of vinyl acetate, parts of butyl acetate and 0.8 of a part ofacetyl peroxide was heated for 13 hours under reflux. During this time.the reflux temperature gradually increased from 93 to 107 C. and thesolution increased in viscosity. There was thus obtained a clear resinsolution of relatively low viscosity from which was isolated, by steamdistillation, a 74% yield of solid resin.

The product was reasonably soft at room temperature and was very soft atC. It was soluble in all common organic solvents except the allphatichydrocarbons. Its properties were such as to recommend it for use as apermanently thermoplastic adhesive.

The same polymer was obtained in somewhat lower yields by carrying outthe reaction at 50:3 C. for 72 hours in the absence of a solvent usingbenzoyl peroxide as a catalyst. Analysis indicated that the final resinwas composed oi 33% by weight of allyl acetate and 67% of vinyl acetate.

Example 2 A solution consisting of 78 parts by weight of allyl caproateand 86 parts of vinyl acetate in 41 parts of toluene, was heated 3 hoursunder reflux in the presence of 4.9 parts of benzoyl peroxide. Thetemperature rose as the polymerization proceeded from 79 to 100 C. andthe viscosity at the solution increased.

The polymer was isolated in an 80% yield by steam distillation of thesolvent and unreacted monomers. It was a light yellow, soft, highlyadhesive resin soluble in all common organic sol vents except petroleumhydrocarbons.

Example 3 A mixture of 10 parts by weight of methallll chloride and 10parts of vinyl acetate was heated under reflux for 11 hours in thepresence of 0.4 of a part of benroyl peroxide. The temperature roseduring this time from 73 to C. and there was obtained a sticky fluidpolymer by steam distillation of the unreacted monomers. The product,which was obtained in a 39% yield, was found to contain 48% of methallylchloride.

Example 4 A solution was prepared by mixing at low temperature in alead-lined pressure vessel, 20 parts by weight of methallyl chloride, 80parts of liquid vinyl chloride and 2 parts of benzoyl de. The reactionwas closed and the solution was heated at 45' C. under agitation for 87hours. The excess vinyl chloride was then allowed to escape andmethallyl chloride was removed by steam distillation. There remained ina 51% yield, a soft resin which contained by analysis 29% or methallylchloride and 71% of vinyl chloride.

Example thus obtained as a strong, clear, white resin in a yield ofabout 54%.

This resin was readily molded at temperatures of 90-l00 C. intocolorless transparent moldings characterized by good stability to light.Dissolved in ketone solvents, it also proved useful in lacquersparticularly where unusual chemical inertness was required, and notablyheat stability A charge consisting of 30 parts by weight of allylacetate, 70 parts of vinyl chloride, 50 parts of acetone and 2 parts ofbenzoyl peroxide was agitated 185 hours at 40 C. in a lead-linedpressure vessel. The resulting gel dissolved readily in acetone fromwhich was precipitated in an 81% yield, a strong white resin containingby analysis of combined allyl acetate and 75% or combined vinylchloride.

A similar charge consisting of 20 parts by weight of allyl-acetate, 80parts of vinyl chloride, 60 parts of acetone and 2 parts oi acetylbenzoyl peroxide was agitated 64 hours at 40 C. The resin isolated asdescribed abov was obtained in a 72% yield.

These resins were readily soluble in ketone. solvents, solutions inwhich they were especially adapted to use in lacquers. Films depositedon iron or tin-plate we're baked minutes at temperatures of 325 F. andabove without addition ing vinyl chloride as a component, decompositionwould have occurred under these conditions.

Example 7 A very similar resin to those described in Example 6 wasobtained by polymerizing together 20. parts of methallyl acetate and 80parts of vinyl chloride in the presence of 1.22 parts of benzoylperoxide in 62 parts of acetone. The resulting resin obtained in 71%yields after 80 hours at 40 C. was soluble in ketones and was otherwisequite similar to the products of Example 6.

Example 8 A mixture of 20 parts by weight of allyl butyrate and 80 partsof vinyl chloride was polymerized in parts of acetone using 2 parts ofbenzoyl peroxide as a catalyst. After 67 hours at 40 C. there wasobtained a 71% yield of strong, clear, white resin very similar to theproducts of Example 6. It was even more easily soluble in ketonesolvents and was characterized by excellent stability to light and heat.

A very similar resin was obtained by polymerizing together under similarconditions 20 parts by weight ofallyl capmate and parts 01 vinylchloride. The resin, obtained in good yields. was very soluble in ketonesolvents and the resulting solutions were satisfactory for use inlacquers.

This is a division of our copending application Serial No. 327,996,flied April 5, 1940, for Conjoint polymerization products.

What we claim is:

1. As a new composition of matter, a resinous product obtained bycomointly polymerizing 50 to 99 parts oi vinyl chloride and 1 to 50parts of allyl acetate.

2. The resinous product oi conjointly polymerizing 50 to 99 parts ofvinyl chloride and allyl l to 50 parts of butyrate.

3. As a new composition of matter. a resinous product obtained byconjointly polymerizing 50 .to 99 parts of vinyl chloride and l to 50parts of of stabilizers and without apparent decomposition an ester ofallyl alcohol and a saturated monoo! the resin. It was found thatfurther increases or safe baking temperatures could be brought about byaddition of suitable stabilizers or stabilizing pigments. In mostcompositions containcarboxylic acid.

. EUGENE W. MOFFETT.

ROY E. SMITH.

